EP0476780B1 - Katalytische Verfahren zur Herstellung verbrückter, Stickstoff enthaltender Verbindungen - Google Patents

Katalytische Verfahren zur Herstellung verbrückter, Stickstoff enthaltender Verbindungen Download PDF

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EP0476780B1
EP0476780B1 EP91202423A EP91202423A EP0476780B1 EP 0476780 B1 EP0476780 B1 EP 0476780B1 EP 91202423 A EP91202423 A EP 91202423A EP 91202423 A EP91202423 A EP 91202423A EP 0476780 B1 EP0476780 B1 EP 0476780B1
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metal oxide
metals
hydroxide
mixed metal
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EP0476780A3 (en
EP0476780A2 (de
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Stephen Wayne King
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a process for preparing bridged nitrogen-containing compounds which comprises contacting a carboxylated cyclic nitrogen-containing compound with a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce the bridged nitrogen-containing compound.
  • Decarboxylation that is, elimination of the -COOH group as CO 2 , is a known process. March, J., Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 1968, pp. 435-436, 477-480 and 878-879, describes various decarboxylation reactions. At pages 435-436, it is stated that aromatic acids can be decarboxylated by heating with copper and quinoline.
  • aliphatic acids which undergo successful decarboxylation have certain functional groups or double or triple bonds in the alpha or beta positions such as malonic acids, alpha-cyano acids, alpha-nitro acids, alpha-aryl acids, alpha-keto acids, alpha-trihalo acids, beta-keto acids, beta,gamma-olefinic acids and the like.
  • oxidative decarboxylation is described in which lead tetraacetate cleaves carboxyl groups, replacing them with acetoxy groups, which may be hydrolyzed to hydroxyl groups.
  • succinic acid derivatives can be bisdecarboxylated with lead tetraacetate.
  • compounds containing geminal carboxyl groups can be bisdecarboxylated with lead tetraacetate, gem-diacetates (acylals) being produced, which are hydrolyzable to ketones.
  • Tundo Pietro et al., Ind. Eng. Chem. Res., 1988, 27, 1565-1571, describes the reaction of dialkyl carbonates with phenols, thiophenols and mercaptans under gas-liquid phase-transfer conditions (continuous flow of gaseous reactants over a solid bed supporting a liquid phase-transfer catalyst) to produce the corresponding ethers and thioethers.
  • the solid bed consisted of potassium carbonate coated with 5 weight percent of CARBOWAX® poly(oxyethylene)glycol 6000 for one set of experiments and alpha-alumina pellets coated with 5 weight percent of potassium carbonate and 5 weight percent of CARBOWAX® poly(oxyethylene)glycol 6000 for another set of experiments.
  • Tundo et al. state at page 1568, right hand column, lines 33-42, that the reaction of alcohols with dialkyl carbonates produces only transesterification.
  • Triethylenediamine also referred to as 1,4-diazabicyclo[2.2.2]octane or DABCO, is an item of commerce which is used as a catalyst for -OH + OCN-reactions to form the urethane linkage in polyurethanes.
  • triethylenediamine may be produced by the method disclosed in WO 87/03592, published June 18, 1987.
  • triethylenediamine may be produced by bringing an amine compound having a specific amino group into contact with a crystalline metal silicate catalyst wherein the molar ratio of silicon dioxide (SiO 2 ) to an oxide of a trivalent metal (M 2 O 3 :M being a trivalent metal) is 12 or more.
  • European Patent Application No. 0158319 discloses a method for preparing 1,4-diazabicyclo[2.2.2]octanes by contacting acyclic or heterocyclic amines with a high-silica zeolite having a silica to alumina ratio of at least 20 to 1.
  • Romanian Socialist Republic Specification 85563 discloses a process for the preparation of triethylenediamine characterized by the fact that N,N-dihydroxyethylpiperazine is cyclized in the gaseous phase on an alumina catalyst alkalized with a base chosen from alkali or alkaline earth hydroxides in an amount of from 0.01-10 weight percent based on alumina at a reaction temperature between 200°C and 550°C, preferably 300°C-450°C, and an operating pressure between 0.1 and 10 atmospheres.
  • WO-A-89/05810 relates to processes for the production of amines, more specifically, to processes for preparing triethylenediamine and/or one or more cyclic or acyclic amines by contacting one or more amine starting materials with one or more molecular sieves.
  • the processes can be varied to alter their selectivity to a number of differing and useful products, including triethylenediamine and substituted triethylenediamines.
  • This invention relates to a process for preparing bridged nitrogen-containing compounds which comprises contacting a carboxylated cyclic nitrogen-containing compound with a mixed metal oxide catalyst under conditions effective to produce the bridged nitrogen-containing compound.
  • This invention also relates to a process for preparing bridged nitrogen-containing compounds which comprises contacting a cyclic nitrogen-containing compound with a CO 2 synthon or a SO 2 synthon in the presence of a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce a bridged nitrogen-containing compound.
  • This invention further relates to a process for preparing bridged nitrogen-containing compounds which comprises (i) contacting a cyclic nitrogen-containing compound with a CO 2 synthon or a SO 2 synthon under conditions effective to produce a carboxylated cyclic nitrogen-containing compound, and (ii) contacting the carboxylated cyclic nitrogen-containing compound with a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce the bridged nitrogen-containing compound.
  • this invention relates to a process for preparing triethylenediamine which comprises contacting 1,4-bis(2-hydroxyethyl)piperazine with dimethyl carbonate in the presence of a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce triethylenediamine.
  • cyclic nitrogen-containing compounds produced in accordance with the processes of this invention are useful for a wide variety of applications such as polyurethane catalysts, acid scavengers and the like.
  • the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.
  • Group IIIB metal oxides embraces the lanthanides and actinides.
  • oxide embraces oxides, hydroxides and/or mixtures thereof.
  • CO 2 synthon embraces SO 2 synthons such as sulfurous acids and sulfurous acid esters.
  • this invention relates to a process for preparing bridged nitrogen-containing compounds which comprises contacting a carboxylated cyclic nitrogen-containing compound with a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce the bridged nitrogen-containing compound.
  • this invention relates to a process for preparing bridged nitrogen-containing compounds which comprises contacting a cyclic nitrogen-containing compound with a CO 2 synthon or a SO 2 synthon in the presence of a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce a bridged nitrogen-containing compound.
  • this invention relates to a process for preparing bridged nitrogen-containing compounds which comprises (i) contacting a cyclic nitrogen-containing compound with a CO 2 synthon or a SO 2 synthon under conditions effective to produce a carboxylated cyclic nitrogen-containing compound, and (ii) contacting the carboxylated cyclic nitrogen-containing compound with a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce the bridged nitrogen-containing compound.
  • this invention relates to a process for preparing triethylenediamine which comprises contacting 1,4-bis(2-hydroxyethyl)-piperazine with dimethyl carbonate in the presence of a mixed metal oxide and/or hydroxide catalyst under conditions effective to produce triethylenediamine.
  • a cyclic nitrogen-containing compound and CO 2 or SO 2 synthon are employed as starting materials, it is believed that a transesterification reaction followed by a decarboxylation reaction occurs to provide the desired bridged nitrogen-containing compound product.
  • the exact reaction mechanism is not fully appreciated but what is appreciated is that a cyclic nitrogen-containing compound starting material and CO 2 or SO 2 synthon starting material can be contacted in the presence of a mixed metal oxide and/or hydroxide catalyst under conditions described herein to provide a bridged nitrogen-containing compound product. It is also appreciated that a carboxylated cyclic nitrogen-containing compound can be contacted with a mixed metal oxide and/or hydroxide catalyst under conditions described herein to provide a bridged nitrogen-containing compound product.
  • Step (i) of certain processes of this invention can in general be referred to as a transesterification reaction.
  • Any suitable transesterification catalyst can be employed in step (i).
  • Such transesterification catalysts are known and include, for example, basic metal oxides, alkoxides and other basic metal salts such as potassium carbonate, sodium titanate and the like.
  • Other suitable transesterification catalysts include, for example, Bronsted acids as sulfuric acid and Lewis acids such as aluminum triisopropoxide.
  • the transesterification catalyst employed in this invention likewise may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst.
  • Both homogeneous and heterogeneous catalysts can be employed in the step (i) reaction.
  • the amount of transesterification catalyst used in step (i) is dependent on the particular catalyst employed and can range from 0.01 weight percent or less to 10 weight percent or greater of the total weight of the starting materials.
  • Suitable cyclic nitrogen-containing compound starting materials which can be employed in the step (i) transesterification reaction include any permissible substituted or unsubstituted cyclic nitrogen-containing compound(s) such as piperazine, substituted piperazine, pyrazine, substituted pyrazine and the like.
  • Preferred cyclic nitrogen-containing compound starting materials include, for example, 1,4-bis(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 1-(2-aminoethyl)piperazine.
  • Illustrative cyclic nitrogen-containing compound starting materials useful in this invention include, for example, piperazine, 1,4-bis(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)piperazine, 1,4-bis-(2-aminoethyl)piperazine, 1-(2-aminoethyl)piperazine and the like.
  • the molar ratio of cyclic nitrogen-containing compound to CO 2 or SO 2 synthon is not narrowly critical and can range from about 0.05:1 or less to about 50:1 or greater, preferably from about 0.1:1 to about 10:1.
  • Suitable CO 2 or SO 2 synthon starting materials which can be employed in the step (i) transesterification reaction include any permissible substituted or unsubstituted carboxyl-containing compound(s) or carbonyl-containing compound(s) which are capable of reacting with a cyclic nitrogen-containing compound under the process conditions described herein, such as those embraced by the formulae R 1 C(O)R 2 or R 1 S(O)R 2 wherein R 1 is hydrogen, halogen, amino, hydroxyl or the residue of an organic compound, and R 2 is amino, hydroxyl or the residue of an organic compound.
  • Illustrative CO 2 synthons include, for example, substituted and unsubstituted carbonates, chlorocarbonates, carbonic acids, carbamates, carbamic acids, oxalates, 2-oxazolidinones, ureas, esters, phosgene, chloroformates, carbon dioxide, orthocarboxylates, sulfurous acids, sulfurous acid esters and the like.
  • carbon monoxide is also considered a CO 2 synthon for appropriate oxidative carbonylation reactions.
  • Preferred CO 2 synthons include, for example, diphenyl carbonate, ethylene carbonate, dimethyl carbonate, 2-oxazolidinone, ethylene sulfite and the like.
  • the use of CO 2 synthons prepared in situ such as the reaction of ethylene carbonate and monoethanolamine to give 2-oxazolidinone is encompassed within the scope of this invention.
  • R 1 and R 2 can be the residue of an organic compound.
  • Illustrative residues of organic compounds include, for example, alkyl, aryl, alkylamino, arylamino, alkyloxy, aryloxy, cycloalkyl, heterocycloalkyl, cycloalkyloxy, heterocycloalkyloxy, alkyloxycarbonyl, aryloxycarbonyl, cycloalkyloxycarbonyl, heterocycloalkyloxycarbonyl, hydroxycarbonyl and the like.
  • the R 1 and R 2 substituents together can complete a cycloalkyl ring or a heterocycloalkyl ring which can be substituted or unsubstituted.
  • the R 1 C(O)R 2 formula is also contemplated to embrace carbon dioxide and carbon monoxide.
  • the step (i) transesterification reaction can be conducted over a wide range of pressures ranging from atmospheric or subatmospheric pressures to superatmospheric pressures. However, the use of very high pressures has not been observed to confer any significant advantages but increases equipment costs. Further, it is preferable to conduct the step (i) reaction at reduced pressures of from 1 mm Hg to less than 760 mm Hg.
  • the step (i) transesterification reaction is preferably effected in the liquid or vapor states or mixtures thereof.
  • the temperature of the step (i) transesterification reaction may be as low as ambient temperature to 300°C.
  • the reaction temperature ranges from 50°C to 200°C, and most preferably from 60°C to 120°C.
  • Suitable carboxylated cyclic nitrogen-containing compounds prepared by the step (i) transesterification reaction include any permissible substituted or unsubstituted carboxylated cyclic nitrogen-containing compounds which are capable of eliminating carbon dioxide under the process conditions described herein, such as carboxylated piperazines, substituted piperazines and the like.
  • Illustrative carboxylated cyclic nitrogen-containing compounds include, for example, bis(methyl 2-piperazinoethyl)carbonate, methyl 2-piperazinoethyl carbonate, phenyl 2-piperazinoethyl carbonate and the like.
  • the amount of carboxylated cyclic nitrogen-containing compound(s) employed in step (ii) is dependent on the amount of mixed metal oxide catalyst employed.
  • the carboxylated cyclic nitrogen-containing compounds prepared by the step (i) transesterification reaction may undergo one or more transesterifications prior to the step (ii) decarboxylation reaction.
  • a hydroxyl-containing compound may be reacted with the originally prepared carboxylated cyclic nitrogen-containing compound under conditions effective to prepare a different carboxylated cyclic nitrogen-containing compound.
  • This invention is not intended to be limited in any manner by the step (i) transesterification reaction.
  • Step (ii) of certain processes of this invention can in general be referred to as a decarboxylation reaction.
  • Suitable decarboxylation catalysts which can be employed in step (ii) include two or more metal oxides.
  • a magnesium:aluminum mixed metal oxide is a preferred mixed metal oxide catalyst as more fully described below.
  • Both homogeneous and heterogeneous catalysts can be employed in the step (ii) reaction.
  • the amount of decarboxylation catalyst used in step (ii) is not narrowly critical and is dependent on whether step (ii) is conducted batchwise or continuously. If batchwise, the catalyst employed can range from 0.01 weight percent or less to 10 weight percent or greater of the total weight of the starting materials. If continuously, generally a fixed bed is employed.
  • Suitable decarboxylation catalysts for use in the processes of this invention comprise mixed metal oxides containing two or more metal oxides.
  • mixed metal oxides include, for example, two or more of the following: Group IA metal oxides, Group IIA metal oxides, Group IIIB metal oxides (including lanthanides and actinides), Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIB metal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VA metal oxides or Group VIA metal oxides.
  • Preferred mixed metal oxides are amphoteric or basic.
  • Preferred mixed metal oxides which may be utilized as decarboxylation catalysts include, for example, two or more oxides of magnesium, aluminum, calcium, strontium, gallium, beryllium, barium, scandium, yttrium, lanthanum, cerium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium, ytterbium, niobium, tantalum, chromium, molybdenum, tungsten, titanium, zirconium, hafnium, vanadium, iron, cobalt, nickel, zinc, silver, cadmium, boron, indium, silicon, germanium, tin, lead, arsenic, antimony and bismuth.
  • Group IIA metal oxides such as magnesium oxide and calcium oxide and Group IIIA metal oxides such as aluminum oxide and gallium oxide are preferred mixed metal oxides for use in this invention.
  • suitable metals in association with magnesium may include, for example, one or more of the following: Group IIIA metals such as boron, aluminum, gallium and indium, Group IIIB metals such as scandium, yttrium and lanthanum including the lanthanides, Group VB metals such as niobium and tantalum, Group VIB metals such as chromium, molybdenum and tungsten, Group VIII metals such as iron, cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IVA metals such as silicon, germanium, tin and lead, Group VA metals such as arsenic, antimony and bismuth, and Group IVB metals such as zirconium and hafnium.
  • suitable metals in association with calcium may include, for example, one or more of the following: Group IIIA metals such as boron, aluminum, gallium and indium, Group IVA metals such as silicon, germanium, tin and lead, Group VB metals such as niobium and tantalum, and Group VIB metals such as chromium, molybdenum and tungsten.
  • Group IIIA metals such as boron, aluminum, gallium and indium
  • Group IVA metals such as silicon, germanium, tin and lead
  • Group VB metals such as niobium and tantalum
  • Group VIB metals such as chromium, molybdenum and tungsten.
  • mixed metal oxides which may be used as decarboxylation catalysts include, for example, MgO-Al 2 O 3 , MgO-SiO 2 , MgO-CdO, MgO-Bi 2 O 3 , MgO-Sb 2 O 5 , MgO-SnO 2 , MgO-ZrO 2 , MgO-BeO, MgO-TiO 2 , MgO-CaO, MgO-SrO, MgO-ZnO, MgO-Ga 2 O 3 , MgO-Y 2 O 3 , MgO-La 2 O 3 , MgO-MoO 3 , MgO-Mn 2 O 3 , MgO-Fe 2 O 3 , MgO-Co 3 O 4 , Mgo-WO 3 , MgO-V 2 O 5 , MgO-Cr 2 O 3 , MgO-ThO 2 , MgO-Na 2
  • the mixed metal oxides described herein which can be used as decarboxylation catalysts may contribute to product selectivity and/or catalytic activity of the reaction and/or stability of the catalyst.
  • the decarboxylation catalyst employed in this invention may also contain support(s), binding agent(s) or other additives to stabilize or otherwise help in the manufacture of the catalyst.
  • the decarboxylation catalysts which comprise two or more metal oxides may be prepared in a wide variety of ways.
  • the two or more metal oxides can be provided from metal salts which can either be heated or precipitated to form the mixed metal oxides.
  • two or more metal oxides may be provided as a partial condensate on a support, such as a silica or alpha, beta or gamma alumina, silicon carbide, and the like, and then condensed by heating to effect polymerization to the desired oxide form.
  • the two or more metal oxides may be condensed from hydrolyzable monomers to the desired oxides, indeed, to form oxide powders which can thereafter be compressed in the presence of a condensation catalyst to form pellets and larger structures of the mixed metal oxide decarboxylation catalyst.
  • a blend of the powders and condensation catalyst can be made into a shapeable paste which can be extruded and cut into pellets according to conventional procedures.
  • the extrudate may thereafter be fired to cure the condensation catalyst and fix the structure.
  • the cut extrudate may be blended with a support material such as those characterized above, and the blend fired to fuse the mixed metal oxide catalyst to the support.
  • a magnesium salt e.g., magnesium nitrate
  • an aluminum salt e.g., aluminum nitrate
  • ammonium hydroxide e.g., ammonium hydroxide
  • the material is then washed with deionized water and calcined at a temperature of from 350°C to 450°C to afford the desired magnesium:aluminum mixed metal oxide catalyst.
  • a magnesium oxide e.g., magnesium carbonate hydroxide pentahydrate
  • an aluminum oxide e.g., aluminum hydroxide hydrate
  • a preferred catalyst structure comprises a Group IIA and IIIA mixed metal oxide having a surface area of at least 100 m 2 /gm which may or may not be bonded to a support material.
  • the decarboxylation catalysts on a support preferably have a surface area greater thank 20 m 2 /gm to as high as 260 m 2 /gm, or greater depending upon which metal oxides are employed.
  • the surface area can be greater than 50 m 2 /gm to as high as 260 m 2 /gm, more preferably, greater than 100 m 2 /gm to as high as 260 m 2 /gm, determined according to the single point N 2 method.
  • support means a solid structure which does not adversely affect the catalytic properties of the catalyst and is at least as stable as the catalyst to the reaction medium.
  • the support can function as a decarboxylation catalyst independent of the mixed metal oxide catalyst used herein, although it may have lower catalytic activity to the reaction.
  • the support may act in concert with the catalyst to moderate the reaction. Some supports may contribute to the selectivity of the reaction.
  • the catalyst structure can comprise from 2 to 60 percent by weight or greater of the support, more preferably from 10 to 50 percent by weight of the support, the remainder being the weight of the mixed metal oxides.
  • the weight of the support is the weight of any binding agent such as phosphates, sulfates, silicates, fluorides, and the like, and any other additive provided to stabilize or otherwise help in the manufacture of the catalyst.
  • the support may be particles as large or larger than the catalyst component and "glued" to the decarboxylation catalyst by virtue of a binding medium.
  • the support may constitute a separate phase in the process of extruding the catalytic structure.
  • the support forming material preferably as a paste is blended with a paste of the decarboxylation catalyst or a partial condensate thereof.
  • the paste may comprise the oxide forms of the support and the decarboxylation catalyst, each blended with water, and/or binding agents.
  • the extrudate of the blend is passed through a multiorificed die and chopped into pellets of the desired sizes.
  • the particles may be doughnut shaped, spherical, and the like. Then the particles are calcined to dry them and complete any condensation reaction in the support and/or the mixed metal oxide decarboxylation catalyst.
  • a preferred group of mixed metal oxide catalysts for use in this invention include materials having the formula: M 2+ / x Q 3+ / y (OH) 2x+3y-nz A n- / z ⁇ a H 2 O wherein M is at least one divalent metal cation; Q is at least one trivalent metal cation; and A is at least one anion providing a valence (n - ), wherein n is at least 1, e.g., between 1 and 4 and most often between 1 and 3, and wherein a is a positive number, M, Q, and A are provided in a proportion such that x/y is a number equal to or greater than 1, z has a value greater than zero and 2x+3y-nz is a positive number.
  • M, Q and A may be selected to provide a layered structure.
  • x/y is in the range of 1 to 12, more preferably x/y is in the range of 1 to 6 and most preferably is in the range of 1 to 4.
  • z has a value such that x/z is between n and 12n, more preferably between n and 6n and most preferably between n and 4n.
  • Suitable divalent metal cations, M broadly include elements selected from the Transition elements and Groups IIA and IVA of the Periodic Table as well as certain Group IIIB elements.
  • Divalent metal cations which are particularly suitable are magnesium, nickel, cobalt, zinc, calcium, strontium and copper.
  • Suitable trivalent metal cations, Q broadly include elements selected from the Transition elements and Groups IIIA and VA of the Periodic Table as well as certain Group IIIB elements.
  • Trivalent metal cations which are particularly suitable can be selected from aluminum, boron, gallium and lanthanum.
  • composition of formula (I) also can include a wide range of anions, A.
  • Any anion or combination of anions which can balance the charge of the cations can be used.
  • Suitable anions include inter alia , halides (such as chloride, fluoride, bromide, and iodide), nitrite, nitrate, sulfite, sulfate, sulfonate, carbonate, chromate, cyanate, phosphite, phosphate, molybdocyanate, bicarbonate, hydroxide, arsenate, chlorate, ferrocyanide, borate, cyanide, cyanaurate, cyanaurite, ferricyanide, selenate, tellurate, bisulfate, as well as organic anions such as oxalate, acetate, hexanoate, sebacate, formate, benzoate, malonate, lactate, oleate, salicylate, stearate, citrate
  • the class of metalate anions described in U.S. Patent No. 4,667,045 including metavanadate, orthovanadate, molybdate, tungstate, hydrogen pyrovanadate and pyrovanadate, also are suitable as anion A.
  • Anions suitable for use in combination with the metal cations previously identified as being particularly suitable are carbonate, halide, phosphate, chromate, sulfate, hydroxide, oxalate, acetate, nitrate, hexanoate, sebacate, vanadate, molybdate, tungstate and ferrocyanate.
  • compositions of formula (I) wherein M is magnesium and Q is aluminum are related to hydrotalcites, while compositions in which M is nickel and A is aluminum are related to takovites.
  • mixed metal oxides prepared using magnesium, nickel or cobalt as the divalent cation and aluminum as the trivalent cation exhibit the typical X-ray diffraction pattern of a hydrotalcite.
  • the processes of this invention can utilize mixed metal oxide catalyst compositions prepared by calcining at an elevated temperature compositions according to formula (I).
  • Suitable calcined compositions have the general formula: M 2+ / x Q 3+ / y (O) (2x+3y-nz)/2 D n- / z wherein M, Q, x, y, z and n have the same meanings defined above in connection with formula (I), and D is at least one nonvolatile anion.
  • Nonvolatile anions may include, inter alia , halides, nitrates, phosphites, phosphate, vanadate, molybdate, tungstate, sulfite, sulfate, chromate, arsenate, borate, chlorate and the like. This list is illustrative and not exclusive.
  • Heat treating the formula (I) compositions to prepare the calcined mixed metal oxide compositions of formula (II) can be done, for example, at a temperature in the range of 200°C to 800°C for a period of time of 12 to 24 hours under an inert atmosphere such as nitrogen or in appropriate cases under an oxidizing atmosphere such as air.
  • Calcination of the mixed metal oxide composition dehydrates the composition and converts at least partially the metal hydroxides to metal oxides. Any nonvolatile anions may be present in the calcined material.
  • the mixed metal oxide can be rehydrated to the mixed metal hydroxide with water. Generally, the mixed metal oxide can be restored readily if the calcination temperature does not exceed 600°C. Mixed metal oxides which are calcined under more severe conditions are not easily rehydrated and lower surface area materials are obtained.
  • compositions falling within formula (I), such as hydrotalcite, which comprises a magnesium-aluminum hydroxide carbonate, and takovite, which comprises a nickel-aluminum hydroxide carbonate, are naturally occurring compositions.
  • such compounds, as well as their related compositions also can be prepared synthetically from inexpensive starting materials using well-known coprecipitation techniques. Procedures for direct synthesis of such materials are described in Itaya et al., Inorg . Chem . (1987) 26 :624-626; Taylor, R.M., Clay Minerals (1984) 19 :591-603; Reichle, U.S. Patent No. 4,476,324; Bish, D.L., Bull.
  • a composition of formula (I) where M +2 is nickel or magnesium, Q +3 is aluminum and An- is carbonate can be prepared by adding, as aqueous solutions, (a) a mixture of nitrates, sulfates or chlorides of nickel or magnesium and aluminum in a desired atomic ratio of nickel or magnesium to aluminum, e.g. 6 atoms of nickel as nickel chloride to 2 atoms of aluminum as aluminum chloride, to (b) an aqueous solution of a stoichiometric amount of sodium hydroxide and a water soluble salt of the desired anion, e.g., sodium carbonate.
  • aqueous solutions (a) a mixture of nitrates, sulfates or chlorides of nickel or magnesium and aluminum in a desired atomic ratio of nickel or magnesium to aluminum, e.g. 6 atoms of nickel as nickel chloride to 2 atoms of aluminum as aluminum chloride, to (b) an aqueous solution of a stoichiometric amount
  • the two solutions are mixed at a temperature of 25°C to 35°C with vigorous stirring over a several-hour period to produce a slurry.
  • the slurry then is heated for 18 hours at a temperature within the range of 50°C to 200°C (preferably between 60°C to 75°C) in order to control crystallization and the ultimate particle size of the resulting crystals.
  • the solids After filtering, and thorough washing and drying, the solids are recovered, typically as a powder.
  • this procedure can be adapted to a wide variety of cations, cation atomic ratios and anion substitutions.
  • water soluble salts of divalent magnesium, cobalt, zinc, copper, iron and calcium can be substituted for the nickel chloride illustrated above, while water soluble salts of trivalent gallium and lanthanum can replace the aluminum chloride.
  • the rate of metal ion addition to the aqueous caustic/anion solution is not critical and can be varied widely.
  • a preferred preparation method is described in Schaper, H. et al., Applied Catalysis , 54, 1989, 79-90.
  • the reaction temperature also is not critical, although the temperature during the reaction preferably is kept below 100°C.
  • An important feature of the procedure is the use of efficient agitation during the mixing procedure to avoid the formation of undesired by-products.
  • Loading of an anion A or D into the mixed metal oxide compositions is influenced by a variety of factors including (i) the amount of anion used in the preparation relative to the metal cations, (ii) the atomic ratio of the metal cations (x/y) in the preparation procedure, (iii) the size of the cations and anions and (iv) the preparation procedure.
  • "loading" is defined as the amount of available valences provided by a desired anion A or D expressed as a percentage of the total available valences for anion A or D.
  • carbonate loading in a hydrotalcite-type catalyst can be maximized by (i) using an excess (e.g., a greater than 3:1 molar ratio) of sodium carbonate to aluminum chloride during catalyst preparation and (2) adjusting the atomic ratio of magnesium to aluminum cations to 2:1.
  • an excess e.g., a greater than 3:1 molar ratio
  • Mixed metal oxide compositions suitable as catalysts also can be prepared from the native or synthetic hydrotalcite-type compositions by ion exchange.
  • hydrotalcite can be treated at ambient conditions with 0.01N phosphoric acid for 18 hours to replace the carbonate anion with phosphate anion.
  • a halide analog of hydrotalcite prepared directly or by anion-exchange could be contacted with molybdic acid or a water soluble salt thereof, or with a water soluble salt of tungstic acid or vanadic acid in order to substitute the transition metal anion for the halide anion in the catalyst structure thereby to produce a mixed metal oxide composition of formula (I).
  • Other ion exchanges will be apparent to those skilled in the art.
  • Calcined mixed metal oxide compositions may exhibit a higher level of selectivity/activity than uncalcined compositions. If a calcined mixed metal oxide catalyst composition experiences any decline in selectivity, it can be regenerated by a heat treatment in the presence of air to restore at least a portion of its initial level of selectivity/activity enhancement and reused. Conditions discussed above for calcining the hydrated mixed metal oxide compositions are suitable for regenerating compositions which have experienced a decline in activity.
  • Catalysts having the formulas (I) and (II) above wherein M is at least one of magnesium and calcium, Q is aluminum or gallium, A is at least one of carbonate, bicarbonate, phosphate, sulfate and nitrate, x/y is between 1 and 20, z has a value which satisfies the relationship: x/z is between n and 12n, and a is a positive number, are generally preferred for vapor phase decarboxylation due to their combination of activity (conversion of precursor) and selectivity.
  • a preferred process involves a vapor phase process using mixed metal oxide catalyst wherein M 2+ is magnesium, Q 3+ is aluminum, A n- is carbonate, x/y is about 1, and z is about 1.
  • the step (ii) decarboxylation reaction may be effected in the liquid or vapor or supercritical liquid states or mixtures thereof.
  • the vapor phase reaction is intended to refer to the general vapor state of the starting materials.
  • the step (ii) decarboxylation reaction conditions may range from subatmospheric or atmospheric to superatmospheric conditions, it is desirable to run the step (ii) reaction from 1 mm Hg to 5,000 mm Hg, preferably from 100 mm Hg to 2,500 mm Hg.
  • the temperature of the step (ii) decarboxylation reaction may be as low as 150°C to 500°C.
  • the reaction temperature ranges from 175°C to 375°C, and most preferably from 225°C to 350°C.
  • Suitable carboxylated cyclic nitrogen-containing compounds for use in the step (ii) decarboxylation reaction can be prepared by the step (i) transesterification reaction or by other methods such as the carbonylation of cyclic nitrogen-containing compounds with carbon monoxide and oxygen at elevated temperatures in the presence of certain copper salts.
  • Such a carbonylation process can be an alternative to the step (i) transesterification reaction and is encompassed within the generic scope of this invention. It is also appreciated that two or more CO 2 synthons can be reacted under conditions effective to produce a carboxylated cyclic nitrogen-containing compound.
  • the step (ii) decarboxylation reaction can be conducted in the presence of an inert diluent which can be either a liquid or gas.
  • an inert diluent which can be either a liquid or gas.
  • a liquid diluent should preferably be a good solvent for the starting materials, inert under the reaction conditions, and of such a nature that separation from the bridged nitrogen-containing compound product will not be difficult.
  • the boiling points of the diluent and the bridged nitrogen-containing compound product should differ by an adequate amount and there should be no tendency of the diluent to form an azeotrope with the desired bridged nitrogen-containing compound product.
  • liquid diluents examples include benzene, toluene, xylene, ethylbenzene, anisole, heptane, octane, nonane, decane, dibutyl ether, and the like. Hydrocarbons are preferred.
  • Illustrative gaseous diluents include for example, nitrogen, methane, hydrogen, carbon monoxide or carbon dioxide.
  • the gaseous diluent should of course be chosen so that it does not prevent the preparation of the desired products.
  • the processes of this invention can be operated using pure starting material(s) as a liquid or gaseous feed.
  • the degree of dilution of the starting materials with various diluents may vary considerably depending upon any process constraints restricting the use of the diluent.
  • the use of very large quantities of some gaseous diluents may be disadvantageous due to the cost of pumping large volumes of the gaseous diluent and increased difficulty in isolating the product, which increase the energy costs of the process.
  • liquid diluents the use of very large quantities may be disadvantageous due to the energy cost associated with large recovery and recycle.
  • the processes of this invention are to be carried out using a gaseous diluent
  • the starting material(s) constitute from 1 to 95, and preferably 5 to 50, mole percent of the starting material/carrier feed.
  • a gaseous diluent such as hydrogen may tend to increase the selectivity of the reaction to the particular products desired.
  • the amount of liquid diluent can vary widely, for instance, from no diluent to 90 weight percent or greater of the total weight of the starting materials.
  • the processes of this invention are useful for preparing substituted or unsubstituted bridged nitrogen-containing compounds such as triethylenediamine, substituted triethylenediamines and the like.
  • Illustrative bridged nitrogen-containing compounds prepared by the processes of this invention include, for example, triethylenediamine, 2-methyl-triethylenediamine and the like.
  • Other illustrative compounds which can be prepared by the processes of this invention include, for example, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene and the like.
  • Suitable bridged nitrogen-containing compounds which can be prepared by the processes of this invention include those permissible bridged nitrogen-containing compounds, including any permissible derivatives of described bridged nitrogen-containing compounds, which are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, 1984.
  • the bridged nitrogen-containing compound products produced by the processes of this invention can be separated by distillation.
  • a crude reaction product can be subjected to a distillation-separation at atmospheric or reduced pressure through a packed distillation column.
  • Reactive distillation may be useful in conducting the step (i) transesterification reaction.
  • the processes of this invention may be carried out using, for example, a fixed bed reactor, a fluid bed reactor, or a slurry reactor.
  • the optimum size and shape of the catalyst will depend on the type of reactor used. In general, for fluid bed reactors, a small, spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so the back pressure within the reactor is kept reasonably low.
  • the processes of this invention can be conducted in a batch or continuous fashion, with recycle of unconsumed starting materials if required.
  • the reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it may be conducted batchwise or continuously in an elongated tubular zone or series of such zones.
  • the materials of construction employed should be inert to the starting materials during the reaction and the fabrication of the equipment should be able to withstand the reaction temperatures and pressures.
  • Means to introduce and/or adjust the quantity of starting materials or ingredients introduced batchwise or continuously into the reaction zone during the course of the reaction can be conveniently utilized in the processes especially to maintain the desired molar ratio of the starting materials.
  • the reaction steps may be effected by the incremental addition of one of the starting materials to the other.
  • reaction steps can be combined by the joint addition of the starting materials to the decarboxylation catalyst.
  • the starting materials can be separated from the bridged nitrogen-containing compound product, for example by distillation, and the starting materials then recycled back into the reaction zone.
  • the processes are conducted for a period of time sufficient to produce the bridged nitrogen-containing compound products.
  • the exact reaction time employed is dependent, in part, upon factors such as temperature, nature and proportion of starting materials, and the like.
  • the reaction time will normally be within the range of from one-half to 100 hours or more, and preferably from less than one to ten hours.
  • the processes may be conducted in either glass lined, stainless steel or similar type reaction equipment.
  • the reaction zone may be fitted with one or more internal and/or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent any possible "runaway" reaction temperatures.
  • Illustrative of permissible reactions encompassed within the scope of this invention include, for example, the following reactant/product combinations: REACTANTS PRODUCT(s) DHEP, DMC TEDA PIP, EC TEDA HEP, DPC TEDA HEP, UR TEDA AEP, UR TEDA HPP, DMC MTEDA PIP, OX TEDA
  • the phrase "residue of an organic compound” is contemplated to include all permissible residues of organic compounds.
  • the permissible residues include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic residues of organic compounds.
  • Illustrative organic compound residues include, for example, alkyl, aryl, cycloalkyl, heterocycloalkyl, alkyl(oxyalkylene), aryl(oxyalkylene), cycloalkyl(oxyalkylene), heterocycloalkyl(oxyalkylene), hydroxyalkyl, hydroxyalkyl(oxyalkylene), hydroxy(alkyleneoxy) and the like.
  • the permissible residues can be substituted or unsubstituted and the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible residues of organic compounds.
  • the term "substituted" is contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which the number of carbons can range from 1 to 20 or more, preferably from 1 to 12.
  • the permissible substituents can be one or more and the same or different for appropriate organic compounds. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds.
  • the contents were stirred at a temperature of 40°C for a period of 40 minutes.
  • the resulting precipitate was filtered and washed (ca. 300 milliliters three to four times) with water at a temperature of 60°C until the pH of the wash was neutral.
  • the filter cake was dried at a temperature of 80°C overnight. The weight of the dried filter cake was about 16 grams.
  • the filter cake was then calcined in air at a temperature of 400°C for a period of 3 hours to afford a magnesium:aluminum mixed metal oxide.
  • a total of 180.0 grams (2.0 mole) of dimethyl carbonate, 17.4 grams (0.1 mole) of 1,4-bis(2-hydroxyethyl)piperazine and 1.0 gram (0.007 mole) of potassium carbonate were combined in a 250 milliliter round bottom flask equipped with a straight distillation head and a magnetic stirrer. The flask contents were heated to reflux under a nitrogen atmosphere. Initial reaction temperatures at reflux were 80°C at the head and 88°C on the kettle. A methanol/dimethyl carbonate azeotrope was removed overhead over a period of 7.5 hours. After this time, the flask contents were cooled and the kettle contents were analyzed by capillary gas chromatography (FlD) using a DB-1701 column.
  • FlD capillary gas chromatography
  • the 1,4-bis(2-hydroxyethyl)piperazine was totally converted to a mixture of methyl bis(2-piperazinoethyl)carbonate and bis(methyl 2-piperazinoethyl)carbonate.
  • the kettle contents were heated for an additional period of 2.5 hours after which the reaction was stopped.
  • the kettle contents were concentrated in vacuo at 20mm Hg and a temperature of 60°C using a rotary evaporator.
  • the major by-products were 1,4-bis(2-hydroxyethyl)piperazine methyl carbonate (ca. 1.5 percent) and bis[1,4-(2-hydroxyethyl)piperazine]carbonate (ca. 9.9 percent).

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Claims (51)

  1. Verfahren zur Herstellung von überbrückten stickstoffhaltigen Verbindungen, umfassend das Zusammenbringen einer carboxylierten cyclischen stickstoffhaltigen Verbindung mit einem Katalysator aus gemischten Metalloxiden, einem Katalysator aus gemischten Metallhydroxiden oder Gemischen davon unter Bedingungen, die wirksam sind, die überbrückte stickstoffhaltige Verbindung zu erzeugen.
  2. Verfahren nach Anspruch 1, wobei die carboxylierte cyclische stickstoffhaltige Verbindung eine substituierte oder unsubstituierte carboxylierte cyclische stickstoffhaltige Verbindung umfaßt.
  3. Verfahren nach Anspruch 1, wobei die carboxylierte cyclische stickstoffhaltige Verbindung Bis(methyl-2-piperazinoethyl)carbonat, Methyl-2-piperazinoethyl-carbonat oder Phenyl-2-piperazinoethylcarbonat umfaßt.
  4. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden zwei oder mehrere Oxide und/oder Hydroxide von Metallen der Gruppe IA, Metallen der Gruppe IIA, Metallen der Gruppe IIIB einschließlich Lanthaniden und Actiniden, Metallen der Gruppe IVB, Metallen der Gruppe VB, Metallen der Gruppe, VIB, Metallen der Gruppe VIIB, Metallen der Gruppe VIII, Metallen der Gruppe IB, Metallen der Gruppe IIB, Metallen der Gruppe IIIA, Metallen der Gruppe IVA, Metallen der Gruppe VA, Metallen der Gruppe VIA umfaßt.
  5. Verfahren nach Anspruch 4, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden zwei oder mehrere Oxide und/oder Hydroxide von Magnesium, Aluminium, Calcium, Strontium, Gallium, Beryllium, Barium, Scandium, Yttrium, Lanthan, Cer, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Lutetium, Ytterbium, Niob, Tantal, Chrom, Molybdän, Wolfram, Titan, Zirkonium, Hafnium, Vanadium, Eisen, Cobalt, Nickel, Zink, Silber, Cadmium, Bor, Indium, Silicium, Germanium, Zinn, Blei, Arsen, Antimon und Wismut umfaßt.
  6. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden mindestens ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA umfaßt.
  7. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIA umfaßt.
  8. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIB umfaßt.
  9. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden Magnesiumoxid und/oder -hydroxid und Aluminiumoxid und/oder -hydroxid umfaßt.
  10. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein gemischtes Metalloxid und/oder -hydroxid mit einer großen Oberflächen umfaßt.
  11. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden eine Oberfläche von mehr als 50 m2/g besitzt.
  12. Verfahren nach Anspruch 6, wobei das Oxid und/oder Hydroxid des Metall der Gruppe IIA 10 bis 90 Gew.-% des Gewichts des Katalysators ausmacht.
  13. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden mit einem Trägermaterial verbunden ist.
  14. Verfahren nach Anspruch 13, wobei der Träger ein Tonerdematerial oder ein Tonerde/Kieselsäure-Material umfaßt.
  15. Verfahren nach Anspruch 13, wobei der Träger ein Kieselsäurematerial oder ein Kieselsäure/Tonerde-Material umfaßt.
  16. Verfahren nach Anspruch 13, wobei der Träger 2 bis 50 Gew.-% des Katalysators aus den gemischten Metalloxiden und/oder -hydroxiden ausmacht.
  17. Verfahren nach Anspruch 1, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden umfaßt:
    (a) ein Material der Formel M 2+ / x Q 3+ / y (OH)2x+3y-nz A n- / z · a H2O wobei M mindestens ein zweiwertiges Metallkation ist, Q mindestens ein dreiwertiges Metallkation ist und A mindestens ein Anion ist, das die Wertigkeit (n-) liefert, wenn n 1 bis 4 ist und wobei a eine positive Zahl ist, M, Q und A in solchen Anteilen vorhanden sind, daß x/y eine Zahl gleich oder größer 1 ist, z einen Wert größer als Null besitzt und 2x+3y-nz eine positive Zahl ist, oder
    (b) ein Material, hergestellt durch Calcinieren des Materials der Formel (I), entsprechend der Formel M 2+ / x Q 3+ / y (O)(2x+3y-nz)/2 D n- / z wobei M, Q, x, y, z und n die gleiche Bedeutung haben, wie oben im Zusammenhang mit Formel (I) angegeben, und D mindestens ein-nicht flüchtiges Anion ist.
  18. Verfahren nach Anspruch 17, wobei x/y eine Zahl zwischen 1 und 12 ist und z einen Wert hat, der der Beziehung: x/z zwischen n und 12n genügt.
  19. Verfahren nach Anspruch 17, wobei A ausgewählt ist aus der Gruppe bestehend aus Carbonat, Halogen, Phosphit, Phosphat, Chromat, Sulfat, Hydroxid, Oxalat, Acetat, Nitrat, Hexanoat, Sebacat, Vanadat, Molybdat, Wolframat und Ferrocyanat.
  20. Verfahren nach Anspruch 17, wobei D ausgewählt ist aus der Gruppe bestehend aus Halogeniden, Phosphit, Phosphat, Vanadat, Molybdat, Wolframat, Sulfit, Sulfat, Chromat, Arsenat, Borat und Chlorat.
  21. Verfahren nach Anspruch 17, wobei x/y eine Zahl zwischen 1 und 6 ist und z einen Wert hat, der der Beziehung: x/z zwischen n und 6n genügt.
  22. Verfahren nach Anspruch 17, wobei das durch Calcinieren des Materials der Formel (I) erhaltene Material bei einer Temperatur im Bereich von 200 bis 800°C während 12 bis 24 Stunden heiß-behandelt worden ist.
  23. Verfahren nach Anspruch 17, wobei M Magnesium und Q Aluminium ist.
  24. Verfahren nach Anspruch 1, wobei die überbrückte stickstoffhaltige Verbindung eine substituierte oder unsubstituierte überbrückte stickstoffhaltige Verbindung umfaßt.
  25. Verfahren nach Anspruch 1, wobei die überbrückte stickstoffhaltige Verbindung Triethylendiamin oder 2-Methyl-triethylendiamin umfaßt.
  26. Verfahren nach Anspruch 1, wobei die carboxylierte cyclische stickstoffhaltige Verbindung hergestellt wird durch Zusammenbringen einer cyclischen stickstoffhaltigen Verbindung mit einem CO2-synthon oder einem SO2-Synthon unter Bedingungen, die wirksam sind zur Erzeugung der carboxylierten cyclischen stickstoffhaltigen Verbindung.
  27. Verfahren nach Anspruch 26, wobei die cyclische stickstoffhaltige Verbindung 1,4-Bis(2-hydroxyethyl)piperazin, 1-(2-Hydroxyethyl)piperazin, Piperazin, 1,4-Bis(2-aminoethyl)piperazin, 1-(2-Aminoethyl)piperazin oder ein Hydropyrazin umfaßt.
  28. Verfahren nach Anspruch 26, wobei das CO2-Synthon oder SO2 -Synthon ein substituiertes oder unsubstituiertes Carbonat, Chlorcarbonat, Carbonsäure, Carbamat, Carbaminsäure, Oxalat, 2-Oxazolidinon, Harnstoff, Ester, Phosgen, Chlorformiat, Kohlendioxid, Orthocarboxylat, Schweflige Säure oder Schwefligsäureester umfaßt.
  29. Verfahren nach Anspruch 26, wobei das CO2-Synthon Dimethylcarbonat, Diphenylcarbonat, Harnstoff oder Ethylencarbonat umfaßt.
  30. Verfahren nach Anspruch 26, wobei die carboxylierte cyclische stickstoffhaltige Verbindung Bis(methyl-2-piperazinoethyl)carbonat, Methyl-2-piperazinoethyl-carbonat oder Phenyl-2-piperazinoethylcarbonat umfaßt.
  31. Verfahren nach Anspruch 26, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden zwei oder mehrere Oxide und/oder Hydroxide von Metallen der Gruppe IA, Metallen der Gruppe IIA, Metallen der Gruppe IIIB, Metallen der Gruppe IVB, Metallen der Gruppe VB, Metallen der Gruppe, VIB, Metallen der Gruppe VIIB, Metallen der Gruppe VIII, Metallen der Gruppe IB, Metallen der Gruppe IIB, Metallen der Gruppe IIIA, Metallen der Gruppe IVA, Metallen der Gruppe VA, Metallen der Gruppe VIA umfaßt.
  32. Verfahren nach Anspruch 31, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden zwei oder mehrere Oxide und/oder Hydroxide von Magnesium, Aluminium, Calcium, Strontium, Gallium, Beryllium, Barium, Scandium, Yttrium, Lanthan, Cer, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Lutetium, Ytterbium, Niob, Tantal, Chrom, Molybdän, Wolfram, Titan, Zirkonium, Hafnium, Vanadium, Eisen, Cobalt, Nickel, Zink, Silber, Cadmium, Bor, Indium, Silicium, Germanium, Zinn, Blei, Arsen, Antimon und Wismut umfaßt.
  33. Verfahren nach Anspruch 26, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden mindestens ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA umfaßt.
  34. Verfahren nach Anspruch 26, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIA umfaßt.
  35. Verfahren nach Anspruch 26, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIB umfaßt.
  36. Verfahren nach Anspruch 26, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden Magnesiumoxid und/oder -hydroxid und Aluminiumoxid und/oder -hydroxid umfaßt.
  37. Verfahren nach Anspruch 26, wobei die überbrückte stickstoffhaltige Verbindung eine substituierte oder unsubstituierte überbrückte stickstoffhaltige Verbindung umfaßt.
  38. Verfahren nach Anspruch 26, wobei die überbrückte stickstoffhaltige Verbindung Triethylendiamin oder 2-Methyl-triethylendiamin umfaßt.
  39. Verfahren zur Herstellung von überbrückten stickstoffhaltigen Verbindungen, umfassend das Zusammenbringen einer cyclischen stickstoffhaltigen Verbindung mit einem CO2-Synthon oder einem SO2-Synthon in Gegenwart eines Katalysators aus gemischten Metalloxiden und/oder -hydroxiden unter Bedingungen, die wirksam sind zur Erzeugung einer überbrückten stickstoffhaltigen Verbindung.
  40. Verfahren nach Anspruch 39, wobei die cyclische stickstoffhaltige Verbindung 1,4-Bis[2-hydroxyethyl)piperazin, 1-(2-Hydroxyethyl)piperazin, Piperazin, 1,4-Bis(2-aminoethyl)piperazin, 1-(2-Aminoethyl)piperazin oder ein Hydropyrazin umfaßt.
  41. Verfahren nach Anspruch 39, wobei das CO2-Synthon oder SO2-Synthon ein substituiertes oder unsubstituiertes Carbonat, Chlorcarbonat, Carbonsäure, Carbamat, Carbaminsäure, Oxalat, 2-Oxazolidinon, Harnstoff, Ester, Phosgen, Chlorformiat, Kohlendioxid, Orthocarboxylat, Schweflige Säure oder Schwefligsäureester umfaßt.
  42. Verfahren nach Anspruch 39, wobei das CO2-Synthon Dimethylcarbonat, Diphenylcarbonat, Harnstoff oder Ethylencarbonat umfaßt.
  43. Verfahren nach Anspruch 39, wobei der Katalysator aus den gemischten Oxiden und/oder Hydroxiden zwei oder mehrere Oxide und/oder Hydroxide von Metallen der Gruppe IA, Metallen der Gruppe IIA, Metallen der Gruppe IIIB, Metallen der Gruppe IVB, Metallen der Gruppe VB, Metallen der Gruppe, VIB, Metallen der Gruppe VIIB, Metallen der Gruppe VIII, Metallen der Gruppe IB, Metallen der Gruppe IIB, Metallen der Gruppe IIIA, Metallen der Gruppe IVA, Metallen der Gruppe VA, Metallen der Gruppe VIA umfaßt.
  44. Verfahren nach Anspruch 43, wobei der Katalysator aus den gemischten Metalloxiden und/oder Hydroxiden zwei oder mehrere oxide und/oder Hydroxide von Magnesium, Aluminium, Calcium, Strontium, Gallium, Beryllium, Barium, Scandium, Yttrium, Lanthan, Cer, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Lutetium, Ytterbium, Niob, Tantal, Chrom, Molybdän, Wolfram, Titan, Zirkonium, Hafnium, Vanadium, Eisen, Cobalt, Nickel, Zink, Silber, Cadmium, Bor, Indium, Silicium, Germanium, Zinn, Blei, Arsen, Antimon und Wismut umfaßt.
  45. Verfahren nach Anspruch 39, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden mindestens ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA umfaßt.
  46. Verfahren nach Anspruch 39, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIA umfaßt.
  47. Verfahren nach Anspruch 39, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIA und ein Oxid und/oder Hydroxid eines Metalls der Gruppe IIIB umfaßt.
  48. Verfahren nach Anspruch 39, wobei der Katalysator aus den gemischten Metalloxiden und/oder -hydroxiden Magnesiumoxid und/oder -hydroxid und Aluminiumoxid und/oder -hydroxid umfaßt.
  49. Verfahren nach Anspruch 39, wobei die überbrückte stickstoffhaltige Verbindung eine substituierte oder unsubstituierte überbrückte stickstoffhaltige Verbindung umfaßt.
  50. Verfahren nach Anspruch 39, wobei die überbrückte stickstoffhaltige Verbindung Triethylendiamin oder 2-Methyl-triethylendiamin umfaßt.
  51. Verfahren nach Anspruch 39, wobei Triethylendiamin hergestellt worden ist aus 1,4-Bis(2-hydroxyethyl)piperazin oder l-(2-Hydroxyethyl)piperazin unter Verwendung von Dimethylcarbonat oder Diphenylcarbonat als CO2-Synthon in Gegenwart eines Katalysators aus gemischten Metalloxiden von Magnesium:Aluminium unter Bedingungen, die wirksam sind zur Erzeugung von Triethylendiamin.
EP91202423A 1990-09-20 1991-09-19 Katalytische Verfahren zur Herstellung verbrückter, Stickstoff enthaltender Verbindungen Expired - Lifetime EP0476780B1 (de)

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US07/585,565 US5194613A (en) 1990-09-20 1990-09-20 Catalytic processes for the preparation of bridged nitrogen-containing compounds
US585565 1990-09-20

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US5466798A (en) * 1992-03-06 1995-11-14 The Regents Of The University Of California Synthesis of lithium aminoborohydrides and reactions thereof
US6160155A (en) * 1999-04-29 2000-12-12 General Electric Company Method and catalyst system for producing aromatic carbonates
DE10061863A1 (de) * 2000-12-12 2002-06-13 Basf Ag Verfahren zur Herstellung von Triethylendiamin (TEDA)
DE10326137A1 (de) * 2003-06-06 2004-12-23 Basf Ag Verfahren zur Erhöhung der Schneidhärte eines Formkörpers enthaltend ein kristallines Alumosilikat und Verwendung dieser Formkörper mit erhöhter Schneidhärte in chemischen Syntheseverfahren, insbesondere in einem Verfahren zur Herstellung von Triethylendiamin (TEDA) durch Umsetzung von Ethylendiamin (EDA) und/oder Piperazin (PIP)
US9150759B2 (en) * 2013-09-27 2015-10-06 Rohm And Haas Electronic Materials Cmp Holdings, Inc Chemical mechanical polishing composition for polishing silicon wafers and related methods
US11820861B2 (en) * 2018-12-21 2023-11-21 Dow Global Technologies Llc Polyether polymerization process

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US4476324A (en) * 1982-06-02 1984-10-09 Union Carbide Corporation Catalyzed aldol condensations
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US5041548A (en) * 1985-12-05 1991-08-20 Idemitsu Kosan Company Limited Method for the preparation of triethylene diamines
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US5194613A (en) 1993-03-16
EP0476780A2 (de) 1992-03-25
KR920006290A (ko) 1992-04-27
CA2051486A1 (en) 1992-03-21
JP2559082B2 (ja) 1996-11-27
JPH04257585A (ja) 1992-09-11
ES2115607T3 (es) 1998-07-01
DE69129350T2 (de) 1998-09-24
US5280120A (en) 1994-01-18
ATE165831T1 (de) 1998-05-15
DK0476780T3 (da) 1998-10-07
MX9101180A (es) 1992-05-04
AU8463591A (en) 1992-03-26

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